From Nonclassical to Classical: Crystallization Seeds Reshape Nucleation Mechanisms
- Univ. of Utah, Salt Lake City, UT (United States)
- Univ. of Utah, Salt Lake City, UT (United States); Weber State Univ., Ogden, UT (United States)
- Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)
- Univ. of Houston, TX (United States)
Crystalline seeds are widely employed in crystallization to accelerate nucleation and control product polymorphs; yet, their impact on nucleation mechanisms remains poorly understood. While homogeneous nucleation of crystals from solution often proceeds through nonclassical pathways involving amorphous intermediates, it is unclear how seeds that promote heterogeneous nucleation reshape these mechanisms and govern polymorph selection. Here, in this study, we provide the first direct evidence that crystalline seeds can bypass the need for amorphous intermediates as nucleation sites, converting nonclassical nucleation mechanisms into classical, monomer-by-monomer crystallization pathways. Using molecular dynamics simulations of zeolite synthesis, we uncover a complex reaction network of competing nucleation processes mediated by intermediate interfacial polymorphs. The interplay between thermodynamic stability and kinetic favorability of these interfacial polymorphs dictates nucleation outcomes, creating a dynamic balance between the interfacial polymorph stability and crystallization rates. Furthermore, we show that the synthesis environment-whether monomers or aggregates serve as reactants-profoundly impacts these pathways. At moderate supersaturation, seeds eliminate amorphous intermediates and promote classical nucleation, whereas high supersaturation or aggregate-based reactants favor nonclassical pathways, even in the presence of seeds. These findings establish a general framework for understanding how seeds govern crystallization mechanisms, with broad implications for controlling nucleation kinetics, polymorph selection, and material properties. While focused on zeolites, this work reveals insights that may be applicable to biominerals, pharmaceuticals, functional materials, and catalysts, providing a basis for engineering crystallization pathways in diverse applications.
- Research Organization:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
- Grant/Contract Number:
- SC0023213; AC02-06CH11357
- OSTI ID:
- 2588397
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 24 Vol. 147; ISSN 0002-7863; ISSN 1520-5126
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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